Characterization of a Proposed Terminal Iron(III) Nitride Intermediate of Nitrogen Fixation Stabilized by a Trisphosphine‐Borane Ligand

Terminal iron nitrides (Fe≡N) have been proposed as intermediates of Fe-mediated nitrogen fixation, and well-defined synthetic iron nitrides have been characterized in high oxidation states, including FeIV, FeV, and FeVI. This study reports the generation and low temperature characterization of a terminally bound iron(III) nitride, P3BFe(N) (P3B=tris(o-diisopropylphosphinophenyl)borane), which is a proposed intermediate of iron-mediated nitrogen fixation by the P3BFe-catalyst system. CW- and pulse EPR spectroscopy (HYSCORE and ENDOR), supported by DFT calculations, help to define a 2A ground state electronic structure of this C3-symmetric nitride species, placing the unpaired spin in a sigma orbital along the B−Fe−N vector; this electronic structure is distinct for an iron nitride. The unusual d5-configuration is stabilized by significant delocalization (≈50 %) of the unpaired electron onto the axial boron and nitrogen ligands, with a majority of the spin residing on boron. © 2022 Wiley-VCH GmbH.